Compounds having the formula



Eitented July 1,

33 REFEEEiGt LDFFICE ooMronNns HAVING THE FORMULA Frank J. soil,Cranford, N. J.

No Drawing. ApplicationAugust 28, 1943, Serial No. 500,449

1 This application is a continuation-in-part of application Serial No.443,304, filed May 16, 1942. This invention relates in general togermicides and in particular to compositions for treating materials suchas textiles, paper, leather, rubber, plastics, coating compositions,soaps, cosmetics, and the like, to render them bacteriostatic andfungistatic and to methods and products in which such compositions areused.

\ qerrnicides for use on materials such as textiles, paper, leather,rubber and the like must be characterized by a number of essentialproperties, the combination of which in a single chemical compound isdifficult to attain. The most essential requisite is that the germicideshould have a high toxicity to fungi and bacteria in very dilutesolution so that the maximum protection will be obtained with a minimumquantity of material. Consequently, it is essential that a germicide fortreating such material should be soluble in a common, inexpensive,readily available solvent, preferably soluble in water or in ethylalcohol, methyl alcohol, and other common solvents. The third essentialcharacteristics for germicides for such materials is that they must benon-irritating to the human skin when used in wearing apparel or incosmetics. Other desirable characteristics in a germicide for suchmaterials is that they should not substantially discolor, or impartundesirable aroma or alter the physical properties such as hand ortensile strength of the treated materials. They should be stable upon along exposure to sunlight and should not chemically react with thetreated materials in an adverse manner. Finally, the treated fabricshould exhibit a substantial laundry fastness. The combination of allthese properties in a single chemical compound is obviously difficult ofattainment.

It is the general object of the present invention to provide a germicidewhich is characterized by having high toxicity to bacteria and fungi inlow concentration, solubility in common solvents and the treated fabricsshould not produce any irritation of the skin.

It is a specific object of the invention to provide a composition fortreating textiles, paper, leather, rubber, and the like to render suchmaterials highly bacteriostatic and fungistatic and which cannot bereadily removed by washing. Another specific object of the invention isto 3 provide compositions and methods for producing materials whichpossess lasting bacteriostatic and 21 Claims. (Cl. 260-434) fungistaticp nerties by reason of the conversion of water soluble compositions towater insoluble compositions.

Other objects of the invention will in part be obvious and will in partappear hereinafter.

According to the present invention, a germicide having all the desiredcharacteristics is produced from organic mercurial compounds whichcontain one or more mercury atoms attached directly to a carboncontaining ring structure and having the following general formula:

R-Hg-X in which R is an aromatic or heterocyclic ring structure to acarbon atom of which the mercury is attached and X is an anion of aninorganic or organic acid. The organic mercury salts having the formulaR-Hg-X are old in the art andno' claim is made herein to such salts perse.

Typical organic mercuric salts which may be used in the practice of thepresent invention are,

'Most of the organic mercury salts having the formula RHgX arerelatively insoluble in water, but as described in application SerialNo. 489,244 filed May 31, 1943, their solubility in aqueous solutions isgreatly increased if ammonium hydroxide and an ammonium salt are presentin the solution. Therefore, I frequently use such ammoniacal solution ofthe salts in the methods herein described.

Applicant ha discovered that the organic mercury salts referred to abovereact with amines to form new addition products. This reaction appearsto be general in character as evidenced by the fact that phenyl mercuryacetate when added to cyclohexylamine, morpholine, pyridine orS-hydroxyquinoline is found to enter into solution momentarily and thento form a precipitate of an insoluble compound. In the case ofcyclohexylamine the resulting product melts at about C. indicating thata new chemical compound has been formed. Moreo ver, the r eaction ineach Search Room case is exothermic thus further indicating thatchemical combination of the reactants has occurred. Applicant hasfurther discovered that if the amines used are themselves water solubleand hydroxylated the resulting addition products are readily soluble inwater and common solvents. It is these new water soluble additionproducts and methods of producing and using the same to which thepresent invention relates Products of the present invention are producedby a reaction which may be represented by the following equation:

ethanolamine, which:are typical ofpthe. reacting compounds which may beemployed, the reaction by which the water soluble addition compositionis producedmay be. represented-by the following equation:

CHQCHZOH CHiCHzOH CHaCOO CHzCHzOH This -compositionmay be produced bysimply dissolving phenyl; mercuric acetate in, triethanole amine at roomtemperature or with moderate heating. The reaction is exothermic and.results in the formation of: a mushy; nearly white prod?" uctofwaxycrystalline character; The addition product has: a melting;pointnor-approximately 75 C. and; is much more soluble in water andalcohol and: much less-soluble in hot benzene than is phenylmercuric-acetate. Thej'solubility of this compound inwaten is increasedby addition of triethanolamine to" the water or by the use of anexcessof triethanolamine; in forming the addition product;

In place of trietha-nolam-ine any other hy droxylalkylamine; mayvbeused. Similarly, other organic mercury salts having the generalformula R,Hg X may be; used and 'ammoniacal solutions orsolutionsofthese saltsin-hydroxyalkylzamines may be employed Thus, by way offurther-illustration; equal molar proportions of phenyl mercuric acetateand monoisopropanolamine, were dissolved in formed-crystals-havingmelting point of 135C...

Products obtained when using monoethanolaminc and diethanolamine formedthick yellowish oils. Other addition products have been producedwhenwusing; triethanolaminec'.and tolylr mercuric; acetate; xylyi;mercuric acetate pyridyl' mcricurict 1.

acetate, phenyl mercuric lactate and phenyl mercuric gluconate. Becauseof the relative insolubility of certain mercury salts, even whenammonium salts and ammonia are used, it is usual to avoid the use of themost, insoluble compounds, such as phenyl mercuric chloride, cyanide andnitrate.

The new products are highly toxic to bacteria and fungi and have beenwidely used in treating textiles, leather, paper, paints, rubber andother products to render them bacteriostatic, fungistatic and mildewresistant.

For most purposes, it is desirable to obtain and use the products in theform of solutions sincethey are then easier to handle and are not soconcentrated that waste of the product will-occur by excessive use incommercial operations. One method which has been used extensively inproducing products in accordance with the present invention is asfollows:

Example I 1500 grams of phenyl mercuric acetate. are mixed with 3750 cc.of triethanolamine. and5'0.0.. cc. of lactic acid. The resulting productis thereafter diluted with water to produce 5 gallons of solution and25. grams of citricacid are dissolved therein. If desired a part, sayone-half. of the water may be mixed withthe triethanolamine beforeaddingthe phenylmercuric acetate thereto. The lactic and citric acidsare not essential tothe process but are found to stabilize the resultingsolution and prevent the forma-- tion of precipitates on longstanding.of the solu-.

. tion.

The solution thus obtained may be-diluted with any desired amount of.water for various commercial applications and uses thereof,.and it! maybe used in the treatment offtextiles, yarn, fibers, paper, leather,rubber, plastics, paints, coating compositions, soaps, cosmetics, andmany other products to render thembacteriostatic, fungistatic' or mildewresistant.

A typical application of the invention-in treating fabric is as.follows:

Example II 17 grams of the solution obtained in Example I areadd'ed toeach gallon of waterin a textile treatingbath. Cotton fabric isthen-passed through the bath and-'is-runwetto squeeze" rolls. adjustedto-leave anamountof liquid in-the fabric iequal to the dryweightthereof. The" fabric isthen said-*to-have pick-up. Thereafter the fabricis dried-omcalender'rolls or a tenter frame runningthrough an-oven or:in any :other suitable way. As brought out'inapplication- Serial No.489-;707fi1edJune4', 1943, heating .of-the novel addition productand-heat-' ing of the fabric aftertreatmentwiththe addi tion product,results in theformationof diphenyl mercury iniandon thefabric.vSincediphenyl-- mercury is almostcompletely insoluble inwaterand othercommon solvents, the-fabric is rendered. permanently bacteriostatic,fungistatic andsmil-e dew resistant.

Instead of heating. the fabric-it may be treated with a sodium,chlorideor othensaltsolution or agent to forma water insoluble phenylmercuricv compound such as phenyl mercuric chloride. thiocyanateoraproduct'of the type described inapplication Serial- 'NO'. 497,548, filedAugust '5, 1943. The fabric'niay also 'be treated in other ways, forexample; as described-"in" application Serial -No;43,304, fil'ed May16,1942; to combine withrcellulose of the. fabric or form an insolubleED REFERENCE reaction product in and on or with the fibers of the fabricso as to render it permanently bacteriostatic and fungistatic andlaundry resistant.

In carrying out the present invention it is not necessary that themercury salt and amine be mixed together in any particularorder andtherefore a solution of the mercury salt may be added to a bathcontaining the amine to produce the addition product inthe bath or thereactants may be brought together in any other desired manner.

Instead of applying the germicidal agent by itself to fabric it may beused in conjunction with any of the usual textile finishes such asstarch vention to provide a germicidal permanent finish on a fabric isas follows:

Example III 1'7 grams of the solution of Example I are added to eachgallon of a bath containing 4% of alkali soluble cellulose ether and 7%of caustic soda. This bath is padded onto the fabric and the fabric thenis passed through squeeze rolls to provide 100% pick-up. Thereafter thefabric is passed through dilute sulfuric acid to coagulate the finishand retain the germicidal product therein. The fabric is finally Washedand dried. If the product is heated after coagulation of the finishdiphenyl mercury is formed in situ whereas treatment of the fabric witha salt solution after coagulation of the finish will cause the insolublephenyl mercury chloride to be produced and retained by the finish.

In place of the cellulose ether finish of the preceding example acellulose finish such as an alka-' line sodium zincate or stannatesolution of the cellulose may be used. Similarly, other conventionaltextile finishing methods may be used to render waterproof or otherfinishes bacteriostatic or fungistatic. Moreover, if the textile finishor both contains triethanolamine or other water soluble amines it isonly necessary to add a solution of the organic mercury compound to thebath to produce the germicidal agent therein.

Products of the present invention have many uses in addition to that oftreating fabrics. Thus they have been applied with success to paper byadding them to the sizing and precipitating or forming an insolublegermicide therein by heating or otherwise. They have also been appliedto leather and are particularly useful in footwear where the productsserve to prevent the growth of bacteria and fungi. When applied tocasein paints and other water paints and when applied to rubber the newproducts have been treated to form insoluble precipitates in thematerial and render the material permanently germicidal.

The invention is not limited to its applications in processes whereinsoluble precipitates are formed from the addition product. They havebeen added to the feed water in the beater of a paper making process toprevent the formation of slime. They also may be used in laundering andwashing processes to prevent mildew and injury to fabrics or othermaterials by the action of bacteria or fungi. They may be added tosoaps, cold creams or to lotions or employed in water solution asantiseptics or fungicides or elsewhere.

These and other. applications and uses of products herein described andthe methods of producing the products are cited by way of example sincemany further uses of the invention and other methods of producing theproducts will be evident or suggest themselves to those skilled in theart. In view thereof it shouldbe understood that the products andprocesses herein particularly described are intended to be illustrativeonly and are not intended to limit the scope of the following claims.

, I claim:

1. A water soluble germicidal and fungicidal compound having thecomposition represented by the formula in which R is an aryl group, R1is a hydroxyalkyl group, R2 and R3 are selected from the groupconsisting of hydrogen, alkyl, and hydroxyalkyl, and X is an anion.

3. A water soluble germicidal and fungicidal compound having thecomposition represented by the formula in which R is an aryl groupcontaining a carbon atom to which the mercury is attached, R1 is ahydroxyalkyl group, and R2 and R3 are selected from the group consistingof hydrogen, alkyl, and hydroxyalkyl.

4. A water soluble germicidal and fungicidal compound having thecomposition represented by the formula N-CHzCHzOH CHafiO 01120112011 5.The method of producing a water soluble germicidal and fungicidalcomposition which comprises the'step of contacting an organic mercurycompound represented by the formula R-I-Ig-X, in which R is a phenylgroup containing a carbon atom to which the mercury is attached and X isan anion, with a water soluble hydroxyalkylamine at substantially roomtemperature and atmospheric pressure.

6. The method of producing a water soluble germicidal and fungicidalcomposition which comprises the step of contacting an organic mercurycompound represented by the formula R-I-Ig-X, in which R is an arylgroup and X is an anion, with a water soluble hydroxyalkylamine atsubstantially room temperature and atmospheric pressure. p

'7. The method of producing a water soluble germicidal and fungicidalcomposition which comprises the step of contacting phenyl mercury searchRoom acetate :with. a water: soluble hydroxyalkylamine at substantiallyroom-temperatureand atmosphericc'pressure.

i8. methodof producing a water soluble germicidal and fungicidalcomposition which comprises the step of contacting phenyl mercuryacetate -.with' triethanolamine at substantially room temperature andatmospheric pressure.

9. The method of producing a water soluble germicidal and fungicidalcomposition which comprises the step of dissolving phenyl mercuryacetate in water containing a molar excess of a water solublehydroxyalkylamine.

10. The method ofproducing a water soluble germicidal and fungicidalcom-position which comprises the step of dissolving phenyl mercuryacetate inwater containing a molar excess of triethanolami-ne.

11; Th'e'method of stabilizing an aqueous solution of a watersolublegermicidal and fungicidal composition produced by dissolving phenylmercury acetate in water containing a molar excess of triethanolamine,which method comprises the stepof adding lactic'acid to said solution.

12. The method of stabilizing an aqueous solution of a Water solublegermicidal and fungicidal composition produced by dissolving phenylmercury acetate in water containing a molar excess of triethanolamine,which method comprises the step of addingflactic acid and citric acid tosaid solution."

'13. Aiwater soluble; germicidal and fungicidal compound having thecomposition represented by theaformulat in which R is a phenyl group, R1is a hydroxyalkyl group, R2 and R3 are selected from the groupconsisting of hydrogen, alkyl, and hydroxyalkyl, and X is an anion.

14; A water "soluble germicidal and fungicidal compound having thecomposition represented by the formula in which Risa-cyclic groupcontain-inga-carbon atom to'which the mercury is-attached, R1 is ahydroxyalkyl -group, and R2 and R3 are selected from-thegroup-consistingof hydrogen, alkyl, and hydroxyalkyl.

l5.-A-new organo-mercurial compound which is readily soluble in waterhaving a melting'point of ab0ut75 C. and characterizedbyits hightoxicity'tobacteria and fungi, which composition is capable o-fbeingproduced by dissolving phenyl mercury acetate inan aqueoussolutioncontaining a'molar excess of triethano-lamin'e at sub stantiallyroom temperature and under atmospheric pressure.

'16. A liquid composition having germicidal and fungicidal propertiescomprising an aqueous solution containing the compound defined in claim2.

17. A liquid composition having germicidal and fungicidal propertiescomprising an aqueous solution containing awater solublehydroxyalkylamine and the'compound defined in claim.2.

181A liquid'composition having germicidal and fungicidal propertiescomprising an aqueous solution containing triethanolamine and thecompound defined in claim'2.

l9. Aliquid'composition having germicidal and fungicidal propertiescomprising an aqueous solution,. a Water soluble hydroxyalkylamine,lactic'acid, and the compound defined in claim 2.

A liquid composition having. germicidal and fungicidal propertiescomprising an aqueous solution containing triethanolamine, lactic acid,and thecompound defined in claim 2.

21. A liquid composition having germicidal and fungicidal propertiescomprising an. aqueous solution containingtriethanolamine, lactic acid,citric acid, and the compound of claim 4.

FRANK J. SOWA.

REFERENCES CITED The followingreferences are of recordin the file ofthis patent:

UNITED STATES PATENTS Number Name 1 Date 978,145 Engelmann Dec. 13, 19102,241,829 Six May 13, 1941

